Electromembrane Processes: Experiments and Modelling

The increasing demand for water and energy poses technological challenges to the implementation of efficient concepts for a sustainable development. In this perspective, electromembrane processes (EMPs) can play a crucial role in green chemistry schemes oriented towards circular economy approaches and renewable energy systems. EMPs are based on the use of ion-exchange membranes under the action of an electric field. Versatility, selectivity, high recovery, and chemical-free operations are their main strengths. Experimental campaigns and modelling tools are prompting the improvement of consolidated processes and the development of novel concepts. Several application fields have been proposed (in chemical, food, pharmaceutical industries, and others) including desalination, water and wastewater treatment, recovery of valuable products, concentration and purification operations, chemical production, and energy production and storage. This book is a collection of the scientific contributions in the Special Issue Processes: Experiments and Modelling from the journal Membranes. It is focused on recent advancements in EMPs and their applications based on the development of cutting-edge engineered systems via experiments and/or models

Bipolar membrane reverse electrodialysis for the sustainable recovery of energy from pH gradients of industrial wastewater: Performance prediction by a validated process model

The theoretical energy density extractable from acidic and alkaline solutions is higher than 20 kWh m-3 of single solution when mixing 1 M concentrated streams. Therefore, acidic and alkaline industrial wastewater have a huge potential for the recovery of energy. To this purpose, bipolar membrane reverse electrodialysis (BMRED) is an interesting, yet poorly studied technology for the conversion of the mixing entropy of solutions at different pH into electricity. Although it shows promising performance, only few works have been presented in the literature so far, and no comprehensive models have been developed yet. This work presents a mathematical multi-scale model based on a semi-empirical approach. The model was validated against experimental data and was applied over a variety of operating conditions, showing that it may represent an effective tool for the prediction of the BMRED performance. A sensitivity analysis was performed in two different scenarios, i.e. (i) a reference case and (ii) an improved case with high-performance membrane properties. A Net Power Density of ~15 W m-2 was predicted in the reference scenario with 1 M HCl and NaOH solutions, but it increased significantly by simulating high-performance membranes. A simulated scheme for an industrial application yielded an energy density of ~50 kWh m-3 (of acid solution) with an energy efficiency of ~80-90% in the improved scenario

Effect of Design Features and Operating Conditions on the Performance of a Bipolar Membrane-Based Acid/Base Flow Battery

In the context of renewable energy sources, storage systems have been proposed as a solution to the issues related to fluctuations in the production and consumption of electric power. The EU funded BAoBaB project is aimed at developing the Acid/Base Flow battery (AB-FB), an environment-friendly, cost-competitive, grid-scale battery storage system based on the cyclic coupling of Bipolar Membrane ElectroDialysis (BMED) and its reverse, the Bipolar Membrane Reverse ElectroDialysis (BMRED) (Pärnamäe et al., 2020). Bipolar membranes promote catalytically water dissociation, thus allowing the storage of electric power in the form of acidic and alkaline solutions (pH gradient), obtained from their corresponding salt (charging mode - BMED), which are then recombined to provide electrical power (discharging mode - BMRED). The membranes are key elements for the process performance; however, the energy conversion efficiency is also affected by the operating parameters of the process and the design features of the stack. In this work, we performed a sensitivity analysis by a mathematical multi-scale model previously developed (Culcasi et al., 2020a). The performance of AB-FB systems was predicted, focusing on the Round Trip Efficiency. Results showed that proper design features made the effect of parasitic currents negligible. Moreover, proper operating conditions maximized the RTE up to 66%

Performance and Perspectives of an Acid/Base Flow Battery

Recently, the utilisation of renewable energy sources is a matter of increasing importance in Europe for Energy Transition and to achieve energy independence. To this aim, tailored Electric Energy Storage (EES) devices must be employed to tackle the issue of fluctuating production from renewables. The Acid/Base Flow Battery (AB-FB) is a cutting-edge technology that allows energy to be stored in the form of acidic and alkaline solutions (van Egmond et al., 2018). This method employs two membrane processes, one for the charge phase and one for the discharge phase, namely Electrodialysis with Bipolar Membrane (EDBM) and Reverse Electrodialysis with Bipolar Membrane (REDBM), respectively. The polymeric membranes and the two electrodes are the main components of this battery. The AB-FB is a novel technology, and a lot of effort is needed to properly assess its current and future potential and identify the geometrical and operating conditions maximising its performance. This study presents a techno-economic analysis (TEA) carried out by using technically optimal results from a previous bi-objective optimisation (Culcasi, et al., 2022b). By assessing the sensitivity on the input parameters, the Levelized Cost of Storage (LCOS) of a battery operating in closed-loop and using current commercial membranes spanned from 0.17 € kWh−1 to 0.45 € kWh−1, indicating that the AB-FB has significant potential in the commercial market

CFD analysis of the fluid flow behavior in a reverse electrodialysis stack

Salinity Gradient Power by Reverse Electrodialysis (SGP-RE) technology allows the production of electricity from the different chemical potentials of two differently concentrated salty solutions flowing in alternate channels suitably separated by selective ion exchange membranes. In SGP-RE, as well as in conventional ElectroDialysis (ED) technology, the process performance dramatically depends on the stack geometry and the internal fluid dynamics conditions: optimizing the system geometry in order to guarantee lower pressure drops (DP) and uniform flow rates distribution within the channels is a topic of primary importance. Although literature studies on Computational Fluid Dynamics (CFD) analysis and optimization of spacer-filled channels have been recently increasing in number and range of applications, only a few efforts have been focused on the analysis of the overall performance of the process. In particular, the proper attention should be devoted to verify whether the spacer geometry optimization really represents the main factor affecting the overall process performance. In the present work, realized within the EU-FP7 funded REAPower project, CFD simulations were carried out in order to assess the effects of different parameters on the global process efficiency, such as the choice of spacer material and morphology, and the optimization of feed and blowdown distribution systems. Spacer material and morphology can affect the fluid dynamics inside each channel. In particular, the appropriate choice of net spacer material can influence the slip/no-slip condition of the flow on the spacer wires, thus significantly affecting the channel fluid dynamics in terms of pressure drops. A Unit Cell approach was adopted to investigate the effect of the different choices on the fluid flow along the channel. Also, the possibility of choosing a porous medium to substitute the net spacer was theoretically addressed. Such investigation focused on the porosity and the fiber radius required to respect the process constrains of pressure drops and mechanical stability. On the other hand, the overall pressure drops of a SGP-RE or ED stack can be considered as resulting from different contributions: the pressure drop relevant to the feed distributor, the pressure drop inside the channel, and the pressure drop in the discharging collector. The choice of the optimal stack geometry is, therefore, strongly related to the need of both minimizing each of the above terms and obtaining the most uniform feed streams distribution among the stack channels. In order to investigate such aspects, simulations were performed on a simplified ideal planar stack with either 50 spacer-less or 50 spacer-filled channels. The effect of the distribution/collector channel thickness and geometry on single-channel flow rates and overall pressure drops in the system was analyzed and a significant influence of distributor layout and size on the overall process performance was found

A comprehensive multi-scale model for bipolar membrane electrodialysis (BMED)

Bipolar membrane electrodialysis (BMED) is a technology combining solute and solvent dissociation to produce chemicals. In the recent decades, it has been typically studied for the production of valuable acid and base solutions from salt streams. Although many works have been devoted to the experimental investigation of BMED, only a few efforts have focused on its mathematical modelling. In the present work, a comprehensive process model based on a multi-scale approach with distributed parameters is presented for the first time. Five models related to four different dimensional scales were fully integrated to form a comprehensive tool. The integrated model was developed by using the process simulator gPROMS Model builder and was based on a semi-empirical approach combining high prediction accuracy and low computational demand. Once validated through a wide range of experimental data, the model capability was shown by carrying out a broad sensitivity analysis assessing the performance of the BMED technology for industrial-scale applications. Results showed how the performance of a BMED unit changes with both varying process conditions and the installed membrane area. Particularly, the non-ideal phenomena that reduce the produced NaOH concentration and increase the energy consumption were thoroughly investigated. Finally, this study demonstrated that a Levelized Cost Of Caustic Soda of about 280 € ton-1NaOH can be obtained, thus making this technology a possible candidate for the industrial production of caustic soda from brines in the future

Heat-transfer performance comparison between overlapped and woven spacers for membrane distillation

Sustainable production of fresh water from seawater desalination is a problem of crucial importance nowadays. Recently, some desalination technologies are taking advantage from the coupling with renewable resources. Among emerging technologies, Membrane Distillation (MD) is considered as one of the most promising as it can be easily powered by solar thermal energy or waste-heat. As an emerging technology, efforts are required to optimize MD unit geometry and operating conditions in order to reduce fresh water production specific cost. Temperature polarization phenomenon is a well-known detrimental effect for the MD process. Spacers are traditionally used to enhance mixing and shrink temperature boundary layers yet yielding higher pressure-losses. The present work is devoted to testing the performance of two different two-layer net-spacers: overlapped and woven. Investigations were carried out by both experiments and Computational Fluid Dynamics (CFD) simulations at different Reynolds numbers ranging from creeping to turbulent flow regime. Experiments (intermediate to high Re) were performed via a novel experimental technique making use of thermochromic liquid crystals and digital image analysis. Computational data (low to intermediate Re) were obtained via steady state (low Re) and Direct Numerical Simulations (intermediate Re), adopting the Unit Cell approach. A good agreement between experiments and CFD data was found in the range of superposition. Results showed that woven spacers guarantee a better mixing than overlapped ones especially in the low-intermediate range of Re thus resulting into a higher Nusselt number. On the other hand, the less disturbed flow field induced by the overlapped wires was found to give raise to lower pumping losses

CFD analysis of concentration polarization phenomena in spacer-filled channels for Reverse Electro-Dialysis

In this work, carried out within the EU-FP7 funded REAPower project, CFD simulations were carried out in order to study the fluid flow behaviour and mass transport phenomena within spacer-filled channels

Limiting current phenomena in electro-membrane processes: local occurrence or stack-dependent one?

Background Electro-membrane processes are gaining great interest in the field of desalination and brine valorisation. However, limiting current phenomena can be a bottleneck for their techno-economic performances. In the present work, the in-out distribution of current density is measured to elucidate the achievement of limiting conditions in real stacks. Materials and Methods A 10-cell pairs Electrodialysis stack (10×40 cm2 active area), equipped with four-segmented electrodes, was tested. NaCl solutions at an inlet concentration ranging from 0.5 to 60 g/l were fed at velocities of either 2 or 4 cm/s in parallel flow. Current density-voltage curves were built by applying equal increasing steps of voltage to each electrode. Outlet concentrations and current efficiency were investigated [1]. Results Figure 1 shows the current density-voltage curves for two couples of inlet concentration. Between the final tract of the ohmic region and the plateau region of the overall stack curve, the current density distribution at the four segments changes markedly. In fact, while at the first electrode the current density continues to increase, at the other three it reaches a maximum and decreases. Thus, as the voltage increases, the current concentrates in a shorter tract of the channel, while it reduces in the remaining part, becoming ineffective for desalination, due to its high resistance. This is caused by the high desalination rate in the first few centimetres, making the dilute conductivity much lower. Moreover, the longer tract of channels at high salinity gradient in the final part of the stack promotes larger diffusion, lowering the current efficiency [2]. Figure 1. Current density-voltage curves for tests at a) Cdil,IN=0.5 g/l and Cconc,IN=30 g/l and b) Cdil,IN=Cconc,IN=1 g/l. Conclusions The attainment of limiting conditions in electrodialysis stacks is strongly related to ohmic phenomena and to the distribution of current density, highlighting its importance in the design of efficient electro-membrane systems. Acknowledgments This work was supported by the SEARcularMINE (Circular Processing of Seawater Brines from Saltworks for Recovery of Valuable Raw Materials) project – Horizon 2020 programme, Grant Agreement no. 869467. The authors are grateful to REDstack B.V. and Fujifilm Manufacturing Europe B.V. for supplying stack and membranes, respectively

A Bi-objective Optimization Study of an Acid-Base Flow Battery for High Efficiency and Improved Power Density

Electrical energy storage is critical for a broader penetration of renewable energies with intermittent nature, such as solar and wind energy. The Acid/Base Flow Battery (AB-FB) is a unique, sustainable, and environmental-friendly storage technology with high electrolyte solution energy density. The method relies on reversible electrodialytic technologies using bipolar membranes to transform electrical energy into chemical energy related to pH gradients and vice versa. The charge phase is accomplished by using bipolar membrane electrodialysis, whereas the discharge phase is performed via bipolar membrane reverse electrodialysis. In a previous work, we developed an advanced multi-scale process model (Culcasi et al., 2021b), revealing the importance of operating conditions and design features for the AB-FB battery performance. For the first time, the current work attempts to optimize the AB-FB. The net Round Trip Efficiency and average net discharge power density were maximized in a two-objective optimization. The ε-constraint method was used to construct curves of Pareto optimal solutions under various scenarios, thereby systematically assessing the effect of decision variables consisting of operating and design parameters. The gPROMS Model Builder® software package's optimization tool was used. This optimization study demonstrated that in a closed-loop configuration, optimized operating conditions and design features can be chosen to maximize net Round Trip Efficiency up to 64% and average net discharge power density up to 19.5 W m-2 using current commercial membranes